Formylmethylene derivatives



Patented July 11, 1939 1. UNITED STATES PATENT OFFICE FORMYLMETHYLENE DERIVATIVES Leslie G. S. Brooker, Rochester, N. Y., assignor, by mesne assignments, to Eastman Kodak Company, Jersey City, N. J., a corporation of New Jersey No Drawing. Application August 13, 1936, Serial No. 95,925. In Great Britain August 15, 1935 Claims.

This invention relates to formylmethylene derivatives and a process for the preparation thereof. The formylmethylene derivatives with which this invention is concerned can be formulated as follows:

and

wherein D represents a vinylene or a phenylene group, R represents an organic residue and Y represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of five-membered and sixmembered heterocyclic nuclei. More particularly, Rcan be an alkyl group, such as methyl, ethyl, n-butyl or n-decyl and the five-membered heterocyclic nucleus can be a thiazole nucleus, such.

Wherein D represents a vinylene or a phenylene group, R represents an alkyl group, R. represents an aryl group of the benzene or naphthalene series, X represents an acid radical, Y represents the non-metallic atoms necessary to complete a five-membered or six-membered heterocyclic nucleus and Z represents hydrogen or an acyl group. More'particularly, R can be an alkyl group, such as methyl, ethyl, n-butyl or n-decyl, X can be an acid radical such as halide, alkylsulfate, p-toluenesulfonate or perchlorate, the five-membered heterocyclic nucleus can be a thiazole nucleus, such as 4-methylthiazole, 4- phenylthiazole, benzothiazole or naphthothiazole, a selenazole nucleus, such as selenazole or benzoselenazole, an oxazole nucleus, such as benzoxazole or naphthoxazole, a thiazoline nucleus, a selenazollne nucleus, or an indolenlne nucleus,

and

such as a 3,3-dialkylindolenine nucleus, and the six-membered heterocyclic nucleus can be a pyridine, a quinoline or a benzoquinoline nucleus. Z can be hydrogen, acetyl, propionyl, benzoyl, naphthoyl or the like. R can be phenyl, naphthyl, toluyl, p-chlorophenyl or the like.

The nature of my new process can be illustrated by the following chemical equation depicting the alkaline hydrolysis of Z-(fl-anilinovinyl) -p-naphthothiazole ethiodide:

NaOH CCH=CHNHC Hs+H20 N l C2115 I Czl is The liberated hydrogen iodideis probably bound as sodium iodide by the sodium hydroxide. The process is advantageously carried out in alkaline media. Sodium and potassium hydroxides and sodium and potassium carbonates being particularly useful alkalies. Heating accelerates the reactions. The hydrolysis can also be carried out in acid media. Strong acids, such as hydrochloric, sulfuric or trichloracetic, are advantageously employed. Acid reacting inorganic salts can be used. In acid media the course of the reaction can probably be illustrated as follows:

N CLlls My new process is especially well adapted to the production of formylmethylene derivatives from benzoxa zole, benzothiazole, naphthothiazole, naphthoxazole, benzoselenazo-le and quinoline B-anilino derivatives. The following examples serve to illustrate but are not intended to limit my invention.

Example 1 1-eihyl-ZJormylmethylene-fi-najrhv thothiazoline I 2- (p-anilinovinyl) -p-naphthothiazole e t h i odide was prepared by fusing an intimate mixture of 2-methyl-p-naphthothiazole ethiodlde (21, g.:

1 mol.) with diphenylformamidine (13.2 g.; 2 mol., l. e., 100% excess) at 150. C. for-about 10 minutes. The product was crushed and washed.

, Example 2,2-methyZ-1-formy lmethylen-beneothiazoline 1.5 g. (1 mol.) of l-(fl-acetanilidovlnyl)-benzothiazole methiodide was hydrolyzed by boiling over a free flame with cc. of hydrochloric acid (1 volume of hydrochloric acid, sp. g. 1.18 with 1 volume of water). After evaporating to dryness, the residue was made alkaline with potassium carbonate and extracted with ether. The combinedextracts gave a residue which was oily and did not lend itself to crystallization readily. It behaved like the above formvlmethylene derivative in its reaction.

Example 32-formyZmethylene-1 -methyl-1 ,Z-dihydroquinoline 3.9 g. (1 mol.) of Z-(p-anilinovinyl) -quinoline methiodide was heated on the steam bath for about 15 minutes with 30 cc. of 95% ethyl alcohol and 30 cc. of 20% aqueous sodium hydroxide. 7

Two layers separated on cooling and the alcoholic layer was concentrated nearly to dryness.

The sticky residue "was dissolved in ether. The other solution dried and the solution concentrated. Solid separated from the concentrate on cooling. It was recrystallized from n-propyl alcohol yielding brownish crystals melting at Example 42-ethy'l-1-formylmethylene-b e n z- 9 ozazoline 4.8 g. (1 mol.) of 2-(5-acetanilidovinyl)-benzoxazoleethiodide was refluxed for about 2 hours with 25 cc. of 95% ethyl alcohol and 10 cc. of water containing 4.0 g. of sodium carbonate. Water (300 cc.) was then added and the whole extracted with ether. On drying the ether solution and evaporating a brownish viscous residue was obtained. The product did not lend itself to ready crystallization but gave the characteristic reactions of formyl-methylene derivatives.

In a similar manner other fi-anilino derivatives can be hydrolyzed to produce formylmethylene derivatives. fl-acetanilido, p-propionanilido, p-benzanilido or the like derivatives can be used. fi-anilinovinyl derivatives can be prepared as illustrated in Example 1. Further description is provided in British Patent 344,409.

These hereindescribed formylmethylene derivatives can be used for the preparation ofmerocarbocyanine' dyes by condensation with heterocyclic compounds containing a reactive methylene group, for example 2-thio-2,4 (3,5)-thiof hydrogen and an acyl group.

azolediones. See the copending application of Leslie G. S.- Brooker Serial No." 95,926 filed August;13, 1936. Thesev hereindescribed formylihethylene derivatives can also be used to prepare carbocyanine dyes by condensing with cyclammonium quaternary salts containing a reactive methyl group. Condensations are advantageously carried out in the presence of a agent, e. g., acetic anhydride.

What I claimas my invention and desire to 'be secured by Letters Patent of the United States of America is:

.1. A product characterized by the following formula: I

wherein A represents a naphthylene group and R represents an alkyl group.

2. A product characterized by the following formula:

C=CHCHO formula:

4. A process comprising hydrolyzing a compound characterized by one of the following forand I R! wherein D represents a radical selected from the group consisting of vinylene and phenylene water-binding groups, R represents an alkyl group, R represents an aryl group. X represents an acid radical, Y representsthe non-metallic atoms necessary ,to complete a heterocyclic nucleus selected from the group consisting of flve-membered and sixmembered heterocyclic nuclei and Z represents a substituent selected from the group consisting 5. A process comprising hydrolyzing,, in the presence of a basic substance, a compound characterized by one of the following formulas:

wherein D represents a radical selected from the group consisting of vinylene and phenylene groups, R represents an alkyl group, R represents an aryl group, X represents an acid radical, Y represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of five-membered and sixmembered heterocyclic nuclei and Z represents a substituent selected from the group consisting oi hydrogen and an acyl group. Y

6. A process comprising hydrolyzlng, in the presence of an acidic substance, a compound characterized by one of the following formulas:

and

wherein D represents a radical selected from the group consisting of vinylene and phenylene groups, R represents an alkyl group, R. represents an aryl group, X represents an acid radical, Y represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of five-membered and sixmembered heterocyclic nuclei and Z represents a substituent selected from the group consisting of hydrogen and an acyl group.

'1. A process comprising hydrolyzing, in the presence of an alkali. a compound characterized by one 01 the following formulas:

and

wherein D represents a radical selected from the group consisting of vinylene and phenylene groups, R represents an alkyl group, R represents an aryl group, X represents an acid radical, Y represents the non-metallic atoms necessary to complete a heterocycllc nucleus selected from the group consisting of flve-membered and six-membered heterocyclic nuclei and Z represents an acyl group.

8. A process comprising hydrolyzing, in the presence of an alkali, a B-anilinovinyl-naphthothiazole alkyl quaternary salt.

9. A process comprising hydrolyzing, in the presence of an alkali, a p-anilinovinyLp-naphthothiazole alkyl quaternary salt.

10. A process comprising hydrolyzing, in the presence of an alkali, a ,S-anilinovinyl-quinoline alkyl quaternary salt.

LESLIE G. S. BROOKER. 

